Gas impermeability for injection molded containers

ABSTRACT

A molded multi-layer article has an interior layer contained within inner and outer layers. The article is molded by co-injecting the inner, outer, and interior layer materials into a mold defining a cavity. The interior layer material is caused to flow along a steam line offset from the zero velocity gradient of the combined material flow in a manner so that the interior layer material flow stream does not flow along or cross the zero velocity gradient yet has a greater flow velocity than the average flow velocity of the combined flow front. These methods and apparatus can mold four or more multilayer articles at once, each having an interior layer extending throughout 95% or more of the sealable portion of the article. The interior layer of a resultant article can extend throughout 99% or more of the sealable portion of the article.

RELATED APPLICATION

The present application is a continuation of U.S. patent applicationSer. No. 13/184,137, filed Jul. 15, 2011, which claims priority to U.S.Provisional Patent Application No. 61/365,303 filed on Jul. 16, 2010.The entire contents of both applications are incorporated herein byreference.

FIELD OF THE INVENTION

The present invention relates to multi-layer injection molded products.In particular, the invention relates to multi-layer molded productshaving gas impermeability or gas scavenger characteristics.

BACKGROUND INFORMATION

Injection molded articles are used for a variety of purposes. Plasticinjection molded products are commonly made from materials such aspolyethylene (PET) or polypropylene (PP). These products resistenvironmental degradation, and are reasonably durable, watertight, andeconomically produced.

However, plastic materials such as PET and PP are gas (e.g., oxygen,nitrogen, etc.) permeable. For applications in which gas permeability isundesirable, for example, food products, medicines and products thatdegrade upon gaseous exposure, a barrier material or scavenger materialis co-injected with the plastic material. Typically, the barriermaterial, such as Ethyl Vinyl Alcohol (EVOH), is injected as an interiorcore material stream between an inner and outer flow stream of the PETor PP material stream, forming an EVOH interior layer inside the PET orPP skin to form the molded product. In order to prevent detrimental gaspermeation, it is necessary that the interior barrier layer extendthroughout substantially the entire portion of the molded article thatis exposed. Even if a very small percentage of the exposed surface arealacks an adequate barrier layer, detrimental amounts of gas permeationmay occur.

In order for the barrier layer to form throughout the molded article, itis necessary that the interior layer material flow to substantially theends of the mold cavity during the molding process. If the interiorlayer material does not flow to the end of the cavity during molding,there will be an inadequate barrier layer at the corresponding “end” ofthe molded product. On the other hand, if the interior layer materialflows too quickly, the interior layer material can penetrate orbreakthrough the flow front or leading edge of the inner and outer layermaterial (i.e., skin), causing undesirable results. Thus, knowntechniques attempt to cause the interior layer material to flow to theends of the mold cavity without breakthrough, e.g., by attempting toprecisely control injection parameters, such as, for example, injectionpressure, temperature, timing, injection location, etc.

Due to significant material flow disparities in non-symmetric moldcavities (i.e., non-symmetric molded articles), this co-injectionprocess has until now been limited to products that are essentiallysymmetrical in shape. However, even symmetrical geometries, whichtheoretically have symmetrical flow characteristics throughout the moldcavity, have met with limited success. Systemic and process variations(e.g., manufacturing tolerances in mold cavity dimensions and surfacefinishes, local temperature variations, injection pressure variations,normally occurring streamline variations, limitations of calculationmethodologies used, etc.) cannot be eliminated using current technologyand can result in either breakthrough or “gaps” (or both) in barrierlayer coverage. Thus, previously known techniques do not provideadequate and/or consistent permeability resistance.

Accordingly, there is a need for methods and apparatuses for forminginjection molded articles having an interior layer where the interiorlayer extends sufficiently throughout the article to adequately preventgas permeation without breakthrough. There is further a need forinjection molded articles containing such a layer.

SUMMARY OF THE INVENTION

Embodiments taught herein address the aforementioned disadvantages ofthe prior art. Exemplary systems, methods and non-transitory computerreadable programs are taught herein to cause an inner core of materialto flow in a manner that results in a molded plastic article withbarrier coverage extending between 95% and 100% of the entire surfacearea. Exemplary systems, methods and non-transitory computer readableprograms can achieve the foregoing barrier coverage in productionmolding using molds that define four or more cavities, eachcorresponding to a resulting molded article, and even operating attypical commercial cycle times. The exemplary systems, methods andcomputer readable programs taught herein are well suited for use informing symmetrical molded plastic articles and asymmetrical moldedplastic articles with barrier coverage extending between 99% and 100% ofthe entire surface area of the sealable portion of the article.

In some embodiments, a plurality of multi-layer articles may be formedby a method of molding. The method may include injecting a firstmaterial into a mold defining a plurality of at least four cavities,each cavity configured to correspond with one of a plurality of at leastfour resulting multi-layer articles. The method may further includeinjecting a second material into the mold to form an inner layer and anouter layer of the plurality of articles. The method may include causingthe first material to flow throughout the mold and form an interiorlayer of each of the plurality of articles, between the inner and outerlayers, and extending through at least 95% of the sealable portion ofeach of the plurality of articles.

In some embodiments, an article may be formed by a method of molding.The method may include injecting a first material into a mold defining acavity. The method may further include injecting a second material intothe mold to form an inner layer and an outer layer of the article. Themethod may include causing the first material to flow throughout themold and form an interior layer of the article, between the inner andouter layers, and extending through at least 99% of the sealable portionof the article.

In embodiments of each of the methods of molding, the mold cavity orcavities and/or the resulting molded article or articles may besymmetric. Embodiments of each of the methods of molding may includeinjecting the first and second materials into the mold cavitysimultaneously. Embodiments of each of the methods may include injectingthe first material into the mold so that it is offset from the zerovelocity gradient of the combined flow of the first and secondmaterials.

In some embodiments, a co-injection molding apparatus may include amold, a plurality of nozzle assemblies, and a processor. The molddefines a plurality of at least four cavities, each cavity configured tocorrespond to one of a plurality of resulting symmetrical multi-layerarticles. Each of the plurality of nozzle assemblies is configured toinject a first polymeric material into the corresponding one of theplurality of cavities to form an interior layer of one of the pluralityof resulting symmetrical multi-layer articles. Each of the plurality ofnozzle assemblies is further configured to inject a second polymericmaterial into the corresponding one of the plurality of cavities to formand inner layer and an outer layer of one of the plurality of resultingsymmetrical multi-layer articles. The processor may be programmed toexecute instructions to cause the first polymeric material to flowthroughout the mold to provide each of the plurality of resultingmulti-layer articles with an interior layer extending through at least95% of the sealable portion of the article.

In some embodiments, a co-injection molding apparatus may include a molddefining a first cavity, a nozzle assembly, and a processor. The nozzleassembly may be configured to inject a first polymeric material into thefirst mold cavity to form an interior layer of a first resultingmulti-layer article. The nozzle may be further configured to inject asecond polymeric material into the first mold cavity to form an innerlayer and an outer layer of the first resulting multi-layer article. Theprocessor may be programmed to execute instructions to cause the firstmaterial to flow throughout the first mold cavity to provide the firstresulting multi-layer article with an interior layer extending throughat least 99% of the sealable portion of the article.

The mold of the foregoing apparatus may further define a plurality ofcavities, each corresponding to one of a plurality of resultingsymmetrical multi-layer articles. The foregoing apparatus may furtherinclude a plurality of nozzle assemblies, each corresponding to one ofthe plurality of cavities. Each of the plurality of nozzle assemblies isconfigured to inject the first polymeric material into the correspondingone of the plurality of cavities to form an interior layer of one of theplurality of resulting symmetrical multi-layer articles. Each of theplurality of nozzle assemblies is further configured to inject thesecond polymeric material into the corresponding one of the plurality ofcavities to form an inner layer and an outer layer of one of theplurality of resulting symmetrical multi-layer articles. The processorof the foregoing apparatus may further be programmed to executeinstructions to cause the first polymeric material to flow throughoutthe plurality of cavities to provide each of the plurality of resultingmulti-layer articles with an interior layer extending through at least99% of the sealable portion of the article.

In embodiments of each of the co-injection molding apparatus, the moldcavity or cavities and/or the molded article or articles may besymmetric. Embodiments of each of the molding apparatus may form as manyas sixty-four multi-layer articles or more per operating cycle.Embodiments of each of the molding apparatus may form multi-layerarticles in a thirty-two by thirty-two cavity stack. Embodiments of eachof the molding apparatus may be configured to inject the inner and outerlayer materials into the mold to form the skin of the resulting articleor articles. Embodiments of the molding apparatus may further beconfigured to inject the interior layer material simultaneously with theinner and outer layer materials into the mold. Embodiments of themolding apparatus may be configured to cause the interior layer materialto be injected so that it is offset from the zero velocity gradient ofthe combined flow of the first and second materials.

In some embodiments, a molded article may have an inner layer, an outerlayer, and an interior layer extending between the inner and outerlayers to at least 99% of the sealable portion of the article. In someembodiments, a molded article may have an inner plastic layer, an outerplastic layer, and an interior plastic layer extending between the innerand outer layers to provide a gas permeation rate of less than about0.05 ppm/day/article when sealed. Embodiments of a molded article mayexhibit gas permeation rates of less than about 0.005 ppm/day/article,or even less than about 0.0005 ppm/day/article when sealed. Embodimentsof either of the foregoing articles may be symmetric. Embodiments ofeither of the foregoing articles may have a circular cross-section alongany transverse plane extending along a sidewall thereof.

In any of the foregoing method, apparatus, article, or non-transitorycomputer readable program embodiments, the interior layer may be offsettoward a surface of the molded article. The interior layer may be afirst material and the inner and outer layers may be a differentmaterial. The interior layer may have a different composition from thematerial of the inner and outer layers. The inner and outer layers maybe a plastic material suitable for injection molding. The interior layermay be substantially gas-impermeable relative to the permeability of theinner and outer layer materials. The interior layer may be a gas barriermaterial comprising a desiccant that absorbs moisture to counteract anyincrease in barrier material permeability caused by increased moisturecontent. The interior layer may be gas-scavenging relative to thescavengability of the inner and outer layer materials.

Other objects and advantages of the various embodiments will becomeapparent in view of the following detailed description of theembodiments and the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic graph showing oxygen permeation as a function ofbarrier coverage.

FIG. 2A is a cross-sectional view of an exemplary container according tovarious embodiments taught herein, but with the wall thickness of thecontainer exaggerated for illustrative purposes.

FIG. 2B is a cross-sectional view along a traverse plane of theexemplary container of FIG. 2A according to various embodiments taughtherein.

FIG. 3 is schematic cross-sectional view of a co-injection moldingsystem according to various embodiments taught herein.

FIG. 4 is a schematic cross-sectional view of an exemplary material flowaccording to various embodiments taught herein.

FIG. 5 is an enlarged view of the flange portion shown in FIG. 1.

FIG. 6 depicts a cross-sectional view of an exemplary molding systemaccording to various embodiments taught herein.

FIG. 7 illustrates an exemplary computing environment suitable forpracticing exemplary embodiments taught herein.

FIG. 8 is a cross-sectional view of the fountain flow effect of acombined polymeric stream as it flows along an annular pathway of a moldcavity.

FIGS. 9A and 9B are cross-sectional views of the velocity profile of thecombined annular flow of the polymeric stream and the relative velocitydifferences across the flow gradient of the combined polymeric stream.

FIG. 9C is a graph illustrating resulting flow fraction and velocityprofile curves across the annular channel within a nozzle such as inFIG. 6 for a plastic flow stream—the ordinate plotting the ratio of flowvelocity-to-average velocity as a function of the radius of the annulusbetween the inner and outer flow channel walls, with the central solidline curve 23 plotting the ratio and showing zero gradient for thecombined flow stream CF, the curve designated with a circle markerplotting the inner flow IF between the radius and the inner cylindricalwall T from the inner to the outer wall, and the curve marked with atriangle plotting the outer flow OF between the outer cylindrical walland the annular radius.

FIG. 10 is a cross-sectional view of an exemplary prior art containerwith the wall thickness of the container exaggerated for illustrativepurposes.

FIG. 11 is a cross-sectional view of an exemplary container according tovarious embodiments taught herein, but with the wall thickness of thecontainer exaggerated for illustrative purposes.

FIG. 12 depicts an exemplary nozzle assembly suitable for practicingembodiments taught herein.

FIG. 13 depicts a cross-sectional view of an exemplary combined materialstream according to various embodiments taught herein.

DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION

FIG. 1 schematically shows an oxygen permeation curve 50 though the wallof a plastic co-injection molded article as a function of coverage of aninterior barrier relative to the total exposed wall surface area of thesealable portion of the article. FIG. 1 also shows a target permeationrate 60 representing an optimal permeation to prevent undesirabledegradation of the substance inside the sealed container. The interiorlayer materials associated with the FIG. 1 graph may consist of EVOH,MXD6 nylon or other passive barrier materials; EVOH, MXD6 nylon or otherbarrier materials, any of which has an oxygen scavenging component; orEVOH, MXD6 nylon or other barrier materials, any of which has adesiccant component. As can be seen in FIG. 1, more than 99% coverage isrequired to achieve the illustrated target permeation rate 60, which is0.005 ppm O₂/day/container (ppm calculated on the basis of liquidcontent of the container). Though the target permeation rate 60 maydepend upon the particular substance in the container, the containerconfiguration, and desired storage life (as total permeation is afunction of rate, exposed area, and time), the illustrated targetpermeation rate 60 is a rate typical of conventional food-containingarticles. Further, while permeation rate is also dependent upon exposureconditions and to some extent, the wall thickness of the container, thepermeation curve 50 is typical of conventional food containers undertypical, if not favorable, storage conditions. Expected variations inthe test parameters produced comparable results.

Depending on the food and the desired storage time (shelf life), thetarget permeation rate 60 may be an order of magnitude higher or lowerthan 0.005 ppm O₂/day/container, i.e., 0.05 or 0.0005 ppmO₂/day/container. The slope of the permeation curve 50 will differ withdifferent types and thicknesses of interior layer materials, but oneskilled in the art will appreciate that a significant increase in thepermeation rate will occur with each 1% decrease in the barrier coverageof the container surface area.

Referring to FIG. 2A, a container 100 has a bottom 105, a sidewall 110extending from the periphery of the bottom 105 to form a chamber 106, inthis embodiment generally cup-shaped or U-shaped, having an open end107, and a flange 115 extending from the periphery of the sidewall 110at the open end 107 of the container. The container 100 in FIG. 2A issymmetrical, meaning that the cross-section of the container 100 alongany transverse plane (i.e., extending horizontally in FIG. 2A) is eithercircular, i.e., through the bottom 105 or flange 115, or annular, i.e.,through the sidewall 110. FIG. 2B illustrates an exemplary symmetricalcross-section, through the bottom 105 of the container 100 of FIG. 2A.

The container 100 includes a sealing zone 180 with a sealable surface.In this embodiment, the sealing zone 180 and its surface extendscircumferentially about the open end 107. In this embodiment the sealingzone 180 and surface are formed in the flange 115. A closure 120, whichmay be of a conventional type, may be sealed to the flange 115 at thesurface of sealing zone 180 by conventional methods, such as byheat-sealing, crimping, threading, and other known methods. Though theillustrative embodiment has a cup-like shape, the invention contemplatescontainers having alternative shapes or configurations in which thesealing zone 180 can be used to seal a portion of the container, whichshould be appreciated by those in the art. For example, if sidewall 110had a lip, the lip could alternatively include the sealing zone and itssurface. Further, though the embodiment of FIG. 2A has an open end 107that may be closed by a closure 120, alternative embodiments withdifferent open ends are contemplated. In the embodiment of FIG. 2, thesurface area of the sealable portion of the molded article comprises thesurface area of the base 105, the surface area of the sidewall 110, andthe surface area of the portion of the flange 115 extending radiallyunder the sealing zone 180 of the closure 120. The surface area of thesealable portion of alternative molded articles may be defineddifferently depending on their shapes or configurations and where theyare sealed or intended to be sealed. For example, the surface area ofthe sealable portion of alternative container embodiments may not extendto a flange, but may instead, for example, extend only to the sealingzone in a lip of the sidewall.

The container 100 may be formed by co-injecting a first plastic materialsuch as, for example, PET or PP and a second plastic material, such as,for example, EVOH, into a mold cavity configured to form a moldedplastic article. The first plastic material forms an inner layer 130 andan outer layer 132, which together generally conform to the desired endshape of the container or article, accounting for manufacturingrequirements (e.g., thermal expansion/contraction) as is known. Thesecond plastic material forms an interior core layer 150. The interiorcore layer 150 may be a barrier layer, a gas scavenging layer, and/or adesiccant layer. Though PET, PP and EVOH are commonly used materials, itshould be understood what other suitable materials may be used, and thatthe various embodiments are suitable for use with other polymericmaterials.

As can be seen in FIG. 2A, the interior layer 150 extends substantiallyentirely throughout the container 100, but is substantially fullysurrounded by the inner layer 130 and the outer layer 132. The innerlayer 130 and the outer layer 132 are known as the skin. As used herein,the term “substantially” or “substantially fully” means 95%-100%coverage of the interior layer across the entire surface area of thecontainer 100.

The gas barrier material of interior layer 150 may be EVOH or othersuitable materials, which are known or may become known, thatsufficiently prevent gases, for example, oxygen, from permeating throughthe container, i.e., from the outside to the inside and vice versa. Ascan be seen in the particular embodiment of FIG. 2A, the inner layer 150extends into the flange 115.

As may be noted, the interior layer 150 in FIG. 2A does not extend tothe end of the flange 115. However, those of ordinary skill in the artshould appreciate that the exposed portion of the flange that does notcontain the interior layer is an extremely small portion of overallexposed surface area of the container 100 (the thickness of the flange115 in FIG. 1 being greatly exaggerated for illustration purposes).Thus, the desired degree of coverage, including high degrees of coverage(e.g., 99% or more), may be obtained without the interior layer 150extending to the outer periphery of the flange 115. Put another way, thedegree of coverage is most relevant to the sealable portion of thecontainer 100 that is within the location where the closure 120 issealed to the container, e.g., the seal contact surface. If an adequatedegree of coverage is achieved within the seal contact surface, e.g.,99% coverage within the seal contact surface, desired permeation ratesmay be achieved. In the illustrated embodiment of FIG. 2A, for example,the interior layer 150 extends to or beyond the margin of the sealcontact surface (in this container configuration the radially inwardmargin of the flange 115), and adequate coverage is obtained without theinterior layer extending beyond that point. Nonetheless, the inventionalso may be utilized to provide the interior layer 150 to or nearly tothe end of flange 115, beyond the seal contact surface margin, asdepicted in dashed lines in FIG. 2A.

The interior layer 150 may be created by co-injecting an interior layermaterial with an inner and outer layer material. Such methods aregenerally known, such as described in U.S. Pat. No. 6,908,581 and thedocuments incorporated therein, each of which is also incorporated byreference herein in its entirety.

As shown schematically in FIG. 3, a mold 200 has mold portions 210 a,210 b that form a mold cavity 220 therebetween. A combined flow 300 froma nozzle assembly is injected into the mold cavity 220 through aninjection gate at gate injection location 140, and the combined flow300, which in certain configurations may be an annular flow, flows fromthe injection location 140 through the mold cavity 220. The combinedflow 300 is formed in the nozzle assembly. The nozzle assembly forms thecombined flow 300 from the inner material, the outer material, and theinterior material. The inner material forms an inner flow, the interiormaterial forms an interior flow and the outer material forms an outerflow of the combined flow 300. The flow of the combined flow 300 forms aflow front 330 that moves through the mold cavity 220. At certain timesegments of flow into the mold, the combined flow 300 may consist of two(inner and outer) materials or three (inner, outer, and interior)materials.

The volumetric flow volume ratio of the inner flow to the outer flowforming the combined flow 300 is selected to cause the interior layerflow stream to flow along a streamline offset from the zero velocitygradient 340 (V_(max)) of the combined flow 300, yet on a streamlinehaving a greater velocity than the average flow velocity (V_(ave)) 360.This prevents the interior layer material flow 150 a from breakingthrough the flow front 330. Rather, as shown in FIG. 4, the interiorlayer material flow 150 a folds over to form a fold over portion 150 bbehind the flow front 330 and remains encased by the inner and outerflows of the combined flow 300. By starting the interior layer materialflow 150 a offset from the zero velocity gradient or shifting theinterior layer material flow 150 a from the zero velocity gradient to aslower moving streamline that has a velocity that is greater that theaverage velocity, the interior layer can “catch up” to the fountain flowand fold over, creating a barrier or scavenger layer that extendsthrough and provides barrier or scavenger protection over a range ofbetween 95% and 100% coverage, or even between 99% and 100% coverage,throughout the sealable portion of the resulting molded plastic article.The interior layer may be located either inside or outside the locationof the zero-velocity gradient creating fold over toward the inside oroutside of the part, respectively.

The present inventor has discovered that such fold over techniques mayunexpectedly be used to mitigate the above-mentioned systemic andprocess variations detrimentally present even in co-injected symmetricarticles. For example, previously known techniques seek to prevent“gaps” in the barrier layer, e.g. caused by the interior layer material150 failing to flow the end of the mold cavity, by controlling theinjection parameters of the interior layer material 150 (e.g., injectiontiming, location, pressure, etc.) so that the interior layer material150 does not lag behind flow front 330. However, as discussed above andin the aforementioned U.S. Pat. No. 6,908,581, this can cause theinterior layer material flow 150 a to break through the flow front 330.Conversely, conventional techniques attempt to avoid breakthrough byutilizing injection parameters that prevent the interior layer materialflow 150 a from catching up to (and breaking through) the flow front330. This, though, can cause the interior layer material flow 150 a tolag too far behind the flow front 330, resulting in inadequate barriercoverage. The inherent systemic and process variations effectivelyprevent this balance from being achieved using previously knowntechniques, producing breakthrough, lagging, or both.

Implementation of a fold over process can mitigate these issues. Using afold over process, the injection parameters can be controlled so thatinterior layer material flow 150 a reaches the end of the mold cavity,for example, a flange forming portion of the cavity, and consequentlysubstantially throughout the resulting molded article withoutbreakthrough concern.

As shown in FIG. 5, as the flow front 330 is approaching the distal end225 of the flange forming portion of the cavity, the interior layermaterial flow 150 a will simply continue to fold over 150 b behind theflow front 330 to the degree necessary to accommodate the surplusinterior layer material flow 150 a. In this manner, a molded productwith adequate barrier coverage, exceeding 99% in symmetric geometries,may be achieved.

FIG. 6 illustrates an exemplary system suitable for practicing exemplaryembodiments. Co-injection molding system 1000 is configured to inject atleast two materials into a mold cavity. Materials suitable for use withthe present invention include polymer based materials such as,Polyethylene Terephthalate (PET), ethylene vinyl alcohol (EVOH), MXD6nylon, polypropylene (PP), and polycarbonates (PC). Co-injection moldingsystem 1000 includes a first material source 1200, a second materialsource 1400, and a manifold 1600. Manifold 1600 may consist of separatemanifolds for each polymeric material. Co-injection molding system 1000further includes nozzle assemblies 18A, 18B, 18C, 18D and mold 2400.Mold 2400 includes gates 20A, 20B, 20C, 20D, and cavities 22A, 22B, 22C,22D. In FIG. 6, each nozzle assembly (18A, 18B, 18C, and 18D) has acorresponding gate and cavity. For example, nozzle assembly 18Acorresponds to gate 20A and cavity 22A.

A first polymeric material is extruded from the first material source1200 and a second polymeric material is extruded from the secondmaterial source 1400 into the manifold 1600 for combining in nozzles18A-18D before being injected into mold cavities 22A, 22B, 22C, 22D. Thefirst and second polymeric streams are combined to form an annularcombined polymeric stream such that the first polymeric material formsan interior core stream in the combined polymeric stream while thesecond polymeric material forms the inner and outer streams in thecombined stream. The inner and outer streams encase the interior corestream as the annular combined polymeric stream is injected from thenozzle.

FIG. 7 illustrates an exemplary computing environment suitable forpracticing exemplary embodiments taught herein. The environment mayinclude a co-injection control device 900 coupled, wired, wirelessly ora hybrid of wired and wirelessly, to co-injection system 1000. Theco-injection control device 900 is programmable to implement executableBarrier Coverage Code 950 for forming a barrier layer and/or scavengerlayer that provides coverage over a range of between 95% and 100%, oreven between 99% and 100%, of a symmetric container or symmetric capsurface area as taught herein. Co-injection control device 900 includesone or more computer-readable media for storing one or morecomputer-executable instructions or software for implementing exemplaryembodiments. The computer-readable media may include, but are notlimited to, one or more types of hardware memory, non-transitorytangible media, etc. For example, memory 906 included in theco-injection control device 900 may store computer-executableinstructions or software, e.g., instructions for implementing andprocessing every module of the executable Barrier Coverage Code 950.Co-injection control device 900 also includes processor 902 and, one ormore processor(s) 902′ for executing software stored in the memory 906,and other programs for controlling system hardware. Processor 902 andprocessor(s) 902′ each can be a single core processor or multiple core(904 and 904′) processor.

Virtualization may be employed in co-injection control device 900 sothat infrastructure and resources in the computing device can be shareddynamically. Virtualized processors may also be used with the executableBarrier Coverage Code 950 and other software in storage 916. A virtualmachine 914 may be provided to handle a process running on multipleprocessors so that the process appears to be using only one computingresource rather than multiple. Multiple virtual machines can also beused with one processor.

Memory 906 may comprise a computer system memory or random accessmemory, such as DRAM, SRAM, EDO RAM, etc. Memory 906 may comprise othertypes of memory as well, or combinations thereof.

A user may interact with co-injection control device 900 through avisual display device 922, such as a computer monitor, which may displaythe user interfaces 924 or any other interface. The visual displaydevice 922 may also display other aspects or elements of exemplaryembodiments, e.g. the databases, the enrollment forms, the medicationguide, etc. Co-injection control device 900 may include other I/Odevices such a keyboard or a multi-point touch interface 908 and apointing device 910, for example a mouse, for receiving input from auser. The keyboard 908 and the pointing device 910 may be connected tothe visual display device 922. Co-injection control device 900 mayinclude other suitable conventional I/O peripherals. Co-injectioncontrol device 900 may further comprise a storage device 916, such as ahard-drive, CD-ROM, or other non-transitory computer readable media, forstoring an operating system 918 and other related software, and forstoring executable Barrier Coverage Code 950.

Co-injection control device 900 may include a network interface 912 tointerface to a Local Area Network (LAN), Wide Area Network (WAN) or theInternet through a variety of connections including, but not limited to,standard telephone lines, LAN or WAN links (e.g., 802.11, T1, T3, 56 kb,X.25), broadband connections (e.g., ISDN, Frame Relay, ATM), wirelessconnections, controller area network (CAN), or some combination of anyor all of the above. The network interface 912 may comprise a built-innetwork adapter, network interface card, PCMCIA network card, card busnetwork adapter, wireless network adapter, USB network adapter, modem orany other device suitable for interfacing authorization computing device900 to any type of network capable of communication and performing theoperations described herein. Moreover, co-injection control device 900may be any computer system such as a workstation, desktop computer,server, laptop, handheld computer or other form of computing ortelecommunications device that is capable of communication and that hassufficient processor power and memory capacity to perform the operationsdescribed herein.

Co-injection control device 900 can be running any operating system suchas any of the versions of the Microsoft® Windows® operating systems, thedifferent releases of the Unix and Linux operating systems, any versionof the MacOS® for Macintosh computers, any embedded operating system,any real-time operating system, any open source operating system, anyproprietary operating system, any operating systems for mobile computingdevices, or any other operating system capable of running on thecomputing device and performing the operations described herein. Theoperating system may be running in native mode or emulated mode.

Barrier Coverage Code 950 includes executable code executable by theprocessor 902 to control the co-injection system 1000 to selectivelycontrol a volumetric flow volume of the inner and outer polymericstreams, control a position of the interior core material stream 150 arelative to a velocity flow front of the combined polymeric stream andcontrol extrusion start time of the interior core stream relative to theextrusion start time of the inner and outer polymeric streams as taughtherein. That is, Barrier Coverage Code 950 includes executable codeexecutable by the processor 902 to control the co-injection system 1000to place the interior core material flow stream 150 a on a flowstreamline that has a velocity that is greater that the average velocityof the combined annular flow 300. Thus, the interior layer material flow150 a can “catch up” to the fountain flow and fold over, creatingcoverage of a barrier layer or scavenger layer in the resulting moldedarticle in a range of between 95% and 100%, or even between 99% and100%, of the sealable portion. Execution of the Barrier Coverage Code950 by the processor 902 allows the co-injection system 1000 to placethe interior layer material flow 150 a either inside or outside thelocation of the zero-velocity gradient creating fold over toward theinside or outside of the resulting article, respectively. Methods andco-injection systems taught herein facilitate the co-injection moldingof food or beverage containers whereby the interior core stream forms astructural element that secures the interior core layer to the innerlayer or the outer layer to prevent delamination of the resulting moldedplastic article and create visual effects in the resulting moldedplastic article without the need for adhesive compounded into thepolymeric materials used to form the resulting molded plastic article.

FIG. 8 depicts the fountain flow effects whereby flowing materialupstream of the flow-front 23 has a velocity gradient 350 such that theflow velocity is fastest in the middle and slowest at or near theinterface of the polymeric stream and the walls of the channels of themold cavity.

FIGS. 9A and 9B depict the velocity gradient 350, where the combinedstream is fastest at point “A” and slower at points “B” or “C”. Thezero-velocity gradient 340 occurs at the point where the velocity of theflow is greatest. Because the flow velocity at the zero-velocitygradient streamline is greater than the average velocity of theflow-front, the interior material injected at or near the zero velocitygradient point can, under some circumstances “catch up” to and pass theflow-front and break through the skin, even if injection of the interiormaterial begins after injection of the inner and outer layers (PET, PC,or PP). The interior core stream material will breakthrough when theinterior material reaches the flow-front of the polymeric stream.

FIG. 9B shows that as the particles initially at points A, B, and Crespectively move downstream, they move farther apart from each otherdue to velocity gradient 350. After a first period of time elapses, theparticles will have moved to new locations designated as A₁, B₁, and C₁respectively. After a second period of time elapses, the particles willhave moved from locations designated as A₁, B₁, and C₁ to new locationsdesignated as A₂, B₂, and C₂ respectively. The relative location of theparticles at the successive times demonstrates the effect of thevelocity gradient 350 over time. Since flow velocity at point A isgreater than the velocity at point B, the particle starting at point Awill move farther over time than the particle starting at point B.Similarly, since flow velocity at point B is greater than the velocityat point C, the particle starting at point B will move farther over timethan the particle starting at point C.

FIG. 9C depicts the normalized velocity profile 350 and volume fractioninside and outside for a fluid with n=0.8 (where n is the parameter forthe non-Newtonian power law model of fluid flow). The hatched area showsthe acceptable location for interior layer placement that is bothgreater than the average velocity and off the zero velocity gradient340. This area will wrap the layer to the inside of the part. From thegraph we can see that the flow fraction of the inside layer can be in arange from 0.1 to 0.45. The flow fraction of the outside layer can befrom 0.9 to 0.55. The interior layer thickness can be as thick as about25% of the thickness of the flowing layer which is about 35% of the flowfraction, 0.1 to 0.45.

FIG. 10 is a cross-section of a container 500 with the leading edge 151of the interior layer having a position typically achieved by the priorart. The leading edge 151 of interior layer 150 has an advanced portion151 c and a lagging portion 151 d. The leading edge 151 of interiorlayer 150 does not reach a portion of the sealing area of the moldedcontainer 500, which may be significant. The interior layer 150 of aprior art container 500 formed under typical production conditions, suchas in a mold defining four or more cavities, does not extend to 95%, andoften much less than 95%, of the surface area of the sealable portion ofthe container. The sealable portion of the container 500 includes thebase 105, the sidewall 110, and the sealing zone within the flange 115.When the entire surface of the prior art container 500 is considered,the portion of the surface area lacking an interior layer is evengreater. The highest interior layer coverage in the prior art was onlyachieved under the best conditions including, for example, the use of amold defining a single symmetrical cavity operating at longer cycletimes. The coverage of the interior layer 150 of a prior art container500 formed under the best conditions, however, still does not match thatof containers in accordance with embodiments taught herein. As shown inFIG. 1, the typical position of interior layer 150 of the prior artcontainer will allow high permeation into the sealed container.

Economical containers require the use of multi-cavity molds operating atfast cycle times. Production molding methods and systems use moldsranging from four cavities to a thirty-two by thirty-two cavity stack(64 cavities total) operating at cycle times of about 5 to 10 seconds.Most systems have cycle times of 5 to 7 seconds depending on part wallthickness. With the prior art, non-uniformities of polymer materialtemperatures, hot runner temperatures and dimensions, mold cavitytemperatures and dimensions, and other factors prevent uniform combinedflow into the mold cavity, resulting in a non-uniform position of theleading edge 151 of the interior layer 150.

FIG. 11 is a cross-section of a container 501 with a leading edge 151 ofan interior layer 150 having a position consistent with embodimentstaught herein. FIG. 11 shows the beneficial effect of using an offset inaccordance with embodiments taught herein to create a foldover 151 bwhen molding parts with the same non-uniformities as described withrespect to the prior art. By offsetting the interior layer 150 from thezero-gradient of the combined flow, the more advanced portion 151 c ofthe interior layer leading edge 151 will begin to foldover withoutbreaking through the flow front. This foldover 151 b of the advancedportion 151 c of the interior leading edge will allow the laggingportion 151 d to reach the flange and provide sufficient radial coverageof the interior layer 150 with respect to the sealing area of theclosure 120.

In production molding using multi-cavity molding systems, the sum of thenon-uniformities in one cavity to any other cavity are different,resulting in different levels in the advanced portion and the laggingportion of the interior layer's leading edge. Embodiments taught hereinovercome the problem of different sums of non-uniformity by creatingmore or less foldover in any one cavity such that the lagging portion ofthe interior layer's leading edge in the most lagging cavity will reachthe required radial position with respect to closure 120. Embodimentstaught herein enable production with molds including four or morecavities, and at cycle times substantially as fast as monolayer molding,while achieving the interior layer leading edge position needed toprovide the target percentage barrier coverage, for example, for foodcontainers.

FIG. 12 illustrates an exemplary nozzle assembly suitable for practicingthe embodiment taught herein. Nozzle assembly 18 includes an innercombining means 30, a middle combining means 32, and an outer combiningmeans 34. Nozzle assembly 18 further includes nozzle body 36 and nozzletip 38. Inner combining means 30, middle combining means 32, outercombining means 34, nozzle body 36, and nozzle tip 38 cooperativelycombine to form a number of conical, annular, and axial passages andchannels in nozzle assembly 18. The nozzle assembly 18 is well suitedfor use in a co-injecting system, for example system 1000, for forming aplastic object having two or more layers.

Inner combining means 30 includes a first inlet 46 to receive a firstpolymeric material 64, such as a skin material (i.e., inner and outerlayer material), and a second inlet 44 to receive a second polymericmaterial 66, such as a core material (i.e., interior layer material).The inner combining means 30 further includes a through bore 40configured to receive a valve pin 42. The through bore 40 extendsthrough the middle combining means 32, and through a portion of theouter combining means 34 to allow the valve pin 42 to move in an axialdirection along a longitudinal axis of the nozzle assembly 18. Throughbore 40 has an inner wall diameter that varies along a centrallongitudinal axis of the nozzle assembly 18. Valve pin 42 is movable inan axial direction along the central longitudinal axis of nozzleassembly 18 to assist in controlling the flow of the first polymericmaterial 64 and second polymeric material 66 through nozzle assembly 18and into mold 24.

Middle combining means 32 cooperatively engages with the inner combiningmeans 30 form a portion of the plurality of annular flow channels innozzle assembly 18. Middle combining means 32 receives from channel 37the first polymeric material 64 and receives from channel 41 the secondpolymeric material 66 to manipulate the flow of each of the polymericmaterials through a plurality of annular fluid carrying passages orchannels. The flow manipulation carried out by middle combining means 32initiates the creation of an outer material stream 58 and an innermaterial stream 56 that together encapsulate an interior material stream60.

The middle combining means 32 when coupled with the inner combiningmeans 30 forms a wrapped-coat-hanger die 31 that circumferentiallyextends around the through bore 40 and valve pin 42. Wrapped-coat-hangerdie 31 provides annular fluid flow passage 48 with a uniform meltdistribution of the first polymeric material 64. Annular fluid flowpassage 48 channels an annular flow stream of the inner material stream56 into stream combination area 54 through an orifice.

Outer combining means 34 cooperatively engages with middle combiningmeans 32 to form one or more fluid carrying passages or channels tomanipulate the second polymeric material 66 forming an interior layer ofthe resulting plastic object. The outer combining means 34 when coupledwith the middle combining means 32 forms a wrapped-coat-hanger die 33that circumferentially extends around inner material stream 56, throughbore 40, and valve pin 42. Wrapped-coat-hanger die 33 provides conicalfluid flow passage 52 with a uniform melt distribution of the secondpolymeric material 66. Conical flow passage 52 feeds an annular streamof the second polymeric material 66 into stream combination area 54through another orifice.

The outer combining means 34 cooperatively engages with nozzle body 36.The outer combining means 34 when coupled with the nozzle body 36 formswrapped-coat-hanger die 35 that circumferentially extends around theinterior layer stream 52, the inner layer stream 56, the through bore40, and the valve pin 42. Wrapped-coat-hanger die 35 provides radialfluid flow passage 50 with a uniform melt distribution of the firstpolymeric material 64. Radial fluid flow passage 50 feeds streamcombination area 54 with a flow of first polymeric material 64 throughan orifice. The first polymeric material 64 fed into the streamcombination area 54 through the orifice forms the outer layer of aresulting molded object.

Fluid flow passages 48, 50, and 52 feed stream combination area 54 withthe outer material stream 58, the inner material stream 56, and theinterior material stream 60. A portion of the nozzle tip 38, a portionof the outer combining means 34, a portion of the middle combining means32, and a portion of the valve pin 42, in combination form the streamcombination area 54. Stream combination area 54 has an inner passagewaydiameter of between about 6.7 mm and about 17.2 mm. Stream combinationarea 54 combines in a simultaneous or near simultaneous manner the outermaterial stream 58 received from the fluid flow passage 50, the innermaterial stream 56 received from the fluid flow passage 48, and theinterior material stream 60 received from the fluid flow passage 52 toform annular output stream.

The channels, bores and passageways of the inner combining means 30, themiddle combining means 32 and the outer combining means 34 and morespecifically the channels, bores and passageways associated with theformation and the flow of inner and outer layer material in the nozzleassembly 18 may be sized, defined, adapted and configured to control orproduce a desired volumetric flow ratio as discussed above. In thismanner, the valve pin 42 may remain in a fixed position and does notneed to be moved to control or form a particular volumetric flow ratio.In other words, the nozzle assembly 18 has a channel configuration andstructure to output a desired or selected volumetric flow ratio withoutthe need of an associated controller or microprocessor. In someexemplary embodiments, the valve pin 42 may be controlled by acontroller or microprocessor to control the volumetric flow ratio.

The annular output stream 49 flows from the stream combination area 54through fluid flow passage 62 to output portion 39 of nozzle assembly18. Fluid flow passage 62 has an annular inner passage that radiallyextends about through bore 40 and axially extends from the streamcombination area 54 to the output portion 39. The output portion 39communicates with a gate of a mold, such as one of gates 20A-20D.

The annular output stream 49 formed by the stream combination area 54has an outer annular skin layer and an inner annular skill) layer formedof the first polymeric material 64, and an interior or core annularlayer formed of the second polymeric material 66. The inner and outerskin layers of the first polymeric material 64 each have a substantiallylike cross sectional area as the materials flow through the fluid flowpassage 62 to the output portion 39. The inner and outer skin layers ofthe first polymeric material 64 encapsulate the interior layer of thesecond polymeric material 66, which forms a core portion of a resultingplastic object.

Upon injection from the nozzle assembly 18, the combined polymericstream 49, as depicted in FIG. 13, comprises an interior stream 55 thatflows along concentric or annular streamlines between the inner 53 andouter 51 polymeric streams.

As may be recognized by those of ordinary skill in the pertinent artbased on the teachings herein, numerous changes and modifications may bemade to the above-described and other embodiments of the presentdisclosure without departing from the spirit of the invention as definedin the appended claims. Accordingly, this detailed description ofembodiments is to be taken in an illustrative, as opposed to a limiting,sense.

1-21. (canceled)
 22. A co-injection molding apparatus comprising: a molddefining a plurality of at least four cavities, wherein each of theplurality of cavities corresponds to one of a plurality of resultingsymmetrical multi-layer articles; a plurality of nozzle assemblies,wherein each of the plurality of nozzle assemblies corresponds to one ofthe plurality of cavities, wherein each of the plurality of nozzleassemblies is configured to inject a first polymeric material into thecorresponding one of the plurality of cavities to form an interior layerof one of the plurality of resulting symmetrical multi-layer articles,and to inject a second polymeric material into the corresponding one ofthe plurality of cavities to form an inner layer and an outer layer ofone of the plurality of resulting symmetrical multi-layer articles; anda processor programmed to execute instructions to cause the firstpolymeric material to flow throughout the mold to provide each of theplurality of resulting symmetrical multi-layer articles with an interiorlayer that extends through at least 95% of a sealable portion.
 23. Aco-injection molding apparatus as defined in claim 22, wherein theprocessor is further programmed to execute instructions to maintain aflow stream of the first polymeric material offset from a zero velocitygradient of a combined material flow throughout each of the plurality ofcavities.
 24. A co-injection molding apparatus as defined in claim 22,wherein each of the plurality of nozzle assemblies are configured tomaintain a flow stream of the first polymeric material offset from azero velocity gradient of a combined material flow throughout thecorresponding one of the plurality of cavities.
 25. A co-injectionmolding apparatus as defined in claim 22, wherein the processor isfurther programmed to execute instructions to cause the first polymericmaterial to flow through each of the plurality of cavities at a greatervelocity than an average velocity of the combined material flow.
 26. Aco-injection molding apparatus as defined in claim 22, wherein theplurality of nozzle assemblies are further configured to cause the firstpolymeric material to flow through each of the plurality of cavities ata greater velocity than an average velocity of the combined materialflow.
 27. A co-injection molding apparatus as defined in claim 22,wherein each of the plurality of cavities is substantially symmetric.28. A co-injection molding apparatus comprising a mold defining a moldcavity, the molding apparatus comprising: a nozzle assembly configuredto inject a first polymeric material into a first mold cavity configuredto form an interior layer of a first resulting symmetrical multi-layerarticle and inject a second polymeric material into the first moldcavity to form an inner and outer layer of the first resultingsymmetrical multi-layer article; and a processor programmed to executeinstructions to cause the first polymeric material to flow throughoutthe first mold cavity to provide the first resulting symmetricalmulti-layer article with an interior layer extending through at least99% of a sealable portion of the first resulting symmetrical multi-layerarticle.
 29. A co-injection molding apparatus as defined in claim 28,wherein the processor is further programmed to execute instructions tomaintain a flow stream of the first polymeric material offset from azero velocity gradient of a combined material flow throughout the firstmold cavity.
 30. A co-injection molding apparatus as defined in claim29, wherein the nozzle assembly is configured to maintain the offset.31. A co-injection molding apparatus as defined in claim 28, wherein theprocessor is further programmed to execute instructions to cause thefirst polymeric material to flow through the first mold cavity at agreater velocity than an average velocity of the combined material flow.32. A co-injection molding apparatus as defined in claim 28, wherein thefirst mold cavity is substantially symmetric.
 33. A co-injection moldingapparatus as defined in claim 28 wherein the mold defines a plurality ofcavities, wherein each of the plurality of cavities corresponds to oneof a plurality of resulting symmetrical multi-layer articles; whereinthe nozzle assembly comprises a plurality of nozzle assemblies, whereineach of the plurality of nozzle assemblies corresponds to one of theplurality of cavities, wherein each of the plurality of nozzleassemblies is configured to inject the first polymeric material into thecorresponding one of the plurality of cavities to form an interior layerof one of the plurality of resulting symmetrical multi-layer articles,wherein each of the plurality of nozzle assemblies is further configuredto inject the second polymeric material into the corresponding one ofthe plurality of cavities to form an inner layer and an outer layer ofone of the plurality of resulting symmetrical multi-layer articles; andwherein the processor is further programmed to execute instructions tocause the first polymeric material to flow throughout the plurality ofcavities to provide an interior layer of each of the plurality ofresulting symmetrical multi-layer articles that extends through at least99% of a sealable portion. 34-50. (canceled)